Red disazo dyes for cotton printing



Patented Mar. 27, 1928.

* stares PATENT oasis VTILHELIVI IIEELLIEIER, F LEVERKUSEN, NEAR COLOGNE, AHD HANS; SCHNEIDER, OF

I STAMMHEIIVI, NEAR COLOGNE, GERMANY, ASSIGNUES T0 GRASSELLI DYESTUFF CORPORATION, OF NEVI YORK, N. Y.. A CORPORATION OF DELAWARE.

RED DISAZO DYES FOR COTTON PRINTING.

No Drawing. Application filed March 23, 1925, Serial No. 17,772, and in Germany April 4, 1924.

Our invention resides in red disazo dyes These dyes are 1-hydroXy2-carboxy-benwhichare particularly useful for the print zoll-azobenzol-3-azo-l-acidyl-amino-S- hying of cotton goods in various red shades of droxy-naphthalene sulfonic acids of the genexceedingly good fastness properties. eral formula in which X stands for one of the numerals l ders, soluble in water with from yellowishand 2. red to bluish-red colors, soluble in concen- It is known thatdiazo-tized amino-benzol trated' sulfuric acid with red colors and azo-salicylic acids can be combined with when reduced as, for instance, with zinc and naphthol sulfonic acids; the resulting dyehydrochloric acid, they yield an aminostufi's dye, however, on chrome inordanted salicylic acid compound, a meta-di-aminocotton goods weak and unpleasant brown benzol compound and an amino-l-acidylshades which, in no way, can be compared amino-8-naphthol sulfonic acid. Printed on with the bright and fast red shades obtained cotton with chromium acetate they produce with our new products. a p various red shades of excellent fastness to Our preferred process for producing these chlorine, washing and light.

new dyestuffs is to couple diazotized aminobenzol-meta-azo-salicylic acids in alkaline tion, the followingexamples are given, the solution with peri-acidyl-amino-naphth0l parts being by weight.

su-lfonic acids. The amino-benzol-meta-azo- Example 13-259 parts meta-amino-bensalicylic acids can be produced by combinzol-azo-salicylic acid are dissolved in hot ing diazotized meta-nitranilines with salicylwater and 115 parts caustic soda B. io acid compounds and reducing the nitro added and cooled to about 5 C; 70 parts group or by diazotizing mono-acidyl-metasodium nitrite dissolved in about 150 parts phenylenediamines, coupling with salicylic water are then added and the mixture run acid compounds and saponifying the acidyl into 350 parts concentrated hydrochloric group. a 1 7 acid, cooled with plenty of ice. The solution Substituted meta-phenylene-diamine compounds such as meta-pl1enylene-diamine sultained in this way is run into 'an ice-cold tonic acid, meta-toluylene-diamine, metasolution of 405 parts Lacetyl-amino-S-naphtoluylene-diamine sulfonic acids, etc., and thol-d-(i-di-sulfonate of sodium dissolved instead of salicylic acids, cresotinic acid, in 2000 parts water to which 200 parts soda salicylic sulfonic acids, etc., can be used in ash ar added. Th coupling is finished in the production of our new type of disazo a few hours, the dyestufi' is salted out, fildyes. The group of peri-acidyl-aminotered, washed and dried. It is a dark red naphthol sulfonic acids mentioned above powder soluble in- Water with a yellowishincludes amongst others,pr0ducts such as red color, soluble in concentrated sulfuric 1-acetyl-amino-8-naphthol-t-sulfonic acid, 1- acid with the same'color. Reduced with zinc acetyhamino-8-naphthol-t-6-di-sulfonic acid, and hydrochloric acid, meta-phenylene-dil -benzol-azninoS-naphthol-3-6--di sulfonic amine, para-amino-sali'cylic acid and aminoacid, 1-acetyl-amino 8 naphthol-3-6-di-sul- 1 acetylamino-8-naphthol-l-6-di sulfonic: fouic acid. acid are obtained. This dyestuff has most Our new dyestuffs are in the form of their probably the formula alkali metal salts generally dark red pow- NH-COOH Printed on cotton with chromium acetate, yellowish-red shades are obtained which are In order to further illustrate our invenof meta-diazo-benzol-azosalicylic acid 010- eXceedin '1 fast to chlorine washin and amino-benzol azo-salic clic acid are now dis- .i a 2: y

light.

Example 2.274 parts oxalyl-Q- l-toluylene-diaminc--sulfonic acid are diazotized in the usual way and the diazo compound solution run into an ice-cold solution of 138 parts salicylic acid in 1000 parts water and 200 parts soda ash. The coupling tempera ture is held at 0 C. and the coupling run for to 12 hours. The mono-aZo-compound is salted out, fitlered off and washed out. The paste is then suspended in 400 parts 30% austic soda. and 2000 parts water.

and boiled for about A an hour which saponifies the oxalyl group. i The excess caustic soda is neutralized with hydrochloric acid and the sulfo-methyl-meta-amino-ben- Zol-aLo-salicylic acid salted out, filtered and dried. It is a yellowish-brown powder soluble in water with yellow color which does not change by additionof n'iineral acid.

351 parts of this sulfo-methyl-1neta- Printed with chromium acetate on cotton goods, a blu1sh-red exceedingly fast. to chlorine, washing and light is obtalned.

in which X stands for one of the numerals 1 and 2 obtainable by combining diazo-benzol-meta-azo-salicylic acid compounds with peri-acidyl-amino-naphthol sulfonic acid, being in form of their alkali metal salts dark red powders soluble in water and in concentrated sulfuric acid with red colors, yielding by reduction with zinc and hydrosolved nois in hot water with the requisite amount of caustic soda cooled to about 5 C. and 70 parts sodium nitrite added. The solution is then'run into ice-cold hydrochloric acid, the diazotization proceeds quickly and the so-obtained diazo solution is now run into an ice-cold solution of 405 parts 1-acetyl-amino-8-naphthol-3-6+di-sulfonate of sodium in 2000 parts of water to which 200 parts of soda ash are added. The coupling is finished after about 5 hours, the color is then salted out, filter-pressed, washed and dried. It is a dark red powder soluble in water with a bluish-red color, soluble in concentrated sulfuric acid with a bluish-red color. Reduced with zinc and hydrochloric acid, fa l-meta-toluylene-diamine-5-sulfonic acid, amino-l-acetyl amino-8-naphthol-3-6 dlisul fonic acid are obtained. The new dyestufi has most likely the following formula SOaH F'Ve claim I V p 1. As new products disazodyes haying most probably the general formula NH-COR(1) 011(8 (80313)):

chloric acid an amino-salicylic acid compound, a ineta-diamino-benzol compound in which X stands for one of the numerals 1 and 2 obtainable by combining diazo-benzol-metamac-salicylic acid compounds in alkaline solution with peri-acidylaminonaphthol sulfonic acids, being in form of their alkali metal salts dark red powders soluble in water and in concentrated sulfuric acid with red colors, yielding by re- H 038 GHa Hois obtainable by combining in alkaline solution Q-diazoJ-methyl-benzol-5-sulfonic and i on NH-CO-CH3 i soin azo-salicylic acid with l-acetyl-amino-S- naphthol-3-6-di-sulfonic acid, being in form chromium acetate fast red of its alkali metal salt a dark red powder soluble in Water and in concentrated sulfuric acid with a bluish-red color, yielding by reduction With zinc and hydrochloric acid, para-amino-salicylic acid, 2-4L-di-aminot0lu0l-5 sulfonic acid and 7-a1nin0-1-acety1- amino-8-naphth0l-3-6-di-sulf0nic acid and yielding when printed on cotton With chromium acetate bluish-red shades of excellent fas'tness t0 chlorine, washing and light. 10

In testimony whereof We have hereunto set our hands.

WILHELM NEELMEIER. HANS SCHNEIDER. 

